Solvent based detergent

ABSTRACT

A solvent based detergent composition consisting essentially of (A) 10-80% liquid aliphatic chlorinated hydrocarbon solvents, (B) 10-40% liquid aliphatic ketones and/or liquid aliphatic esters, (C) 6 to 50% water soluble liquid alkanols having two to five carbon atoms and (D) 1-10% surface active agents.

United States Patent Geiss et al.

1*Dec. 24, 1974 SOLVENT BASED DETERGENT Inventors: Richard Geiss, Lusshof, 8875 Offingens, 1 Donau; R011 Quarch, St. Johannsstrasse 37, 7912 Weissenhorn, both of Germany Notice: The portion of the term of this patent subsequent to June 5, 1990, has been disclaimed.

Filed: Apr. 12, 1973 Appl. No.: 350,393

Related US. Application Data Continuation-impart of Ser. No. 60,924, Aug. 4, 1970, Pat. No. 3,737,386.

Foreign Application Priority Data Aug. 6, 1969 Germany 1940018 US. Cl 252/162, 134/38, 252/71, 252/D1G. 8, 252/DIG. 10

Int. Cl C09d 9/04 Field of Search 252/162, 170, 171; 134/38, 134/40 Primary Examiner-William E. Slchulz Attorney, Agent, or Firm-Littlepage, Quaintance, Murphy & Dobyns [57] ABSTRACT A solvent based detergent composition consisting essentially of (A) 10-80% liquid aliphatic chlorinated hydrocarbon solvents, (B) 1040% liquid aliphatic ketones and/or liquid aliphatic esters, (C) 6 to 50% water soluble liquid alkanols having two to five carbon atoms and (D) 110% surface active agents.

14 Claims, No Drawings SOLVENT BASED DETERGENT This application is a continuation in part of application 60,924, filed Aug. 4, 1970 now U.S. Pat. No. 3,737,386, granted June 5, 1973.

The invention relates to industrial detergents based on a combination of organic solvents in admixture with cleansing intensifiers.

It has long been known to utilize a number of different mixtures of solvents for industrial cleaning, in particular combinations of trichloroethylene or perchloroethylene in admixture with benzenes or aromatics such as benzene, toluene and xylene. In general these substances are used for removing fat and varnish.

For several cleaning processes, however, detergents of the known prior art have proved to be insufficient, particularly for cleaning construction units, e.g. tiles in service stations, tunnels, railway stations and similar buildings, soiled concrete areas and other cemented surfaces.

The dirt on walls and floors of such buildings consists of tars, greases, oils, rosins, resins, asphaltenes, set paints and varnishes as well as of mechanical impurities.

It is impossible to solve such dirt accumulations and wash them away with water immediately without a long residence time and without applying mechanical power such as scrubbing and rubbing. The same is true with soiled tools, e.g. brushes, etc.

Accordingly, it is an aim of the present invention to provide a detergent composition comprising in combination several solvents which can be applied even at high levels of impurity, i.e., which exhibit good solving properties and which make it possible to wash away the lubricants composed of dirt (tars, greases, oils, rosins, resins, etc.).

The new detergents are organic liquid or solvent mixtures which can be mixed with water and consist of:

A. 10-80%, preferably 10-25%, by weight liquid aliphatic chlorinated hydrocarbons;

10-40%, preferably 25-40%, by weight liquid lower aliphatic ketones and/or liquid lower aliphatic esters;

C. 5-50%, preferably 40-50%, by weight watersoluble liquid alkanols having 2-5 carbon atoms; and

D. 1-10% by weight of a detergent anionic or nonionic surface active agent.

These compositions may also contain E. l-l%, preferably 57%, by weight liquid hydrocarbon fraction having a boiling point of 120 to 180 C.

As a result of practical experiments the preferred percentages of the components, A, B, C, and D in the compositions according to the invention are considered optimal. From the economic point of view they are also optimal. A reduction of A would cause a longer cleaning time and a reduction of the synergetic effect which means a reduction of the detregency power of the composition.

The percentage of A can be increased from 25-80% by weight which causes an increase of the detergency power, especially if methylene chloride is used.

The combined percentage of B and C can be reduced only to 25% by weight without reducing the detergency power as well. If the percentage of B and C is increased to more than 75 -80% the detergency power is diminished, too.

The percentage of component D should remain within the limits of 1-10% by weight. Smaller amounts reduce the wetting and emulsifying power far too much, whereas using higher amounts produce no additional benefits.

Preferred use is made of mixtures of components of the above groups consisting of A. methylene chloride, trichloroethylene, and perchloroethylene;

B. methyl ethyl ketone and ethyl acetate;

C. isopropanol, propanol and brutanol;

D. an anionic surface active agent; and

E. a benzene fraction.

Additionally, the following substances individually or in admixture with other representatives of the same groups may be used as components of the groups consisting of A. as chlorinated hydrocarbons: monochloromethane, trichloroethane and tetrachloromethane, 1,1- and 1,2-dichloromethanes, 1,1,1 and 1,1,2- trichloroethanes, and 1,1,],2- and l,1,2,2- tetrachloroethanes;

B. as esters: methyl acetate, propyl acetates and butyl acetates, as well as the corresponding propionates and butyrates including ethyl esters;

as ketones: diethyl, methyl propyl and isomeric ethyl butyl ketones. The esters and ketones are completely interchangeable and they preferably have 3-8 carbon atoms;

C. as alkanols: ethanol and amyl alcohols;

D. as anionic surface active agents: sulphates and ether sulphates and sulfonates of fatty alcohols and fatty acids alkyl sulphonates, aryl alkyl sulphonates and alkyl aryl sulphonates, ethylene oxide adducts, e.g. sodium lauryl sulphates, lauryl alcohol surfurce acid ester and triethyanolamine salts of ether sulphates of fat alcohols; and as nonionic surface active agents: nonionic detergents having polyoxyethylene hydrophilic groups and oil soluble fatty acid, alcohol, amide or amine groups.

They produce above all a high degree of detergency and make it possible that the treated areas can be washed clean with water.

In order to prove the efficiency of the composition of the invention comparative tests were conducted using compositions which did not contain chlorinated hydrocarbons or the surface active substances. However, these test compositions produced insufficient cleaning results.

All amounts of the ingredients listed in the following examples are by weight. With the compositions of the test examples 1 and 2 and the examples 1 to 7 pottery tiles were cleaned which had been soiled successively with the substances a to e listed below in the Test comparison report and which had then been submitted to the ageing process described in that report.

Test 1: Test compositions without surface active substances.

The test compositions had the following ingredients:

A. 10% methylene chloride 20% methyl ethyl ketone 20% ethyl acetate 50% isopropanol B. methylene chloride 10% methyl ethyl ketone 15% ethyl acetate 5% isopropanol ln the absence of a surface active substance the lubricants formed by dirt and solvent from the test composition could not be washed away with water from the soiled areas or could not be washed away completely. Dirt stripes remained which could be removed only after various applications of the solvent while rubbing or by means of other mechanical powers. Test 2: Test composition without a chlorinated hydrocarbon.

The mixture had the following ingredients:

25% methyl ethyl ketone 2571 ethyl acetate 40% isopropanol 10% of an anionic surface active substance. B. 45% methyl ethyl ketone 25% ethyl acetate 25% isopropanol of an anionic surface active agent.

In the absence of a chlorinated hydrocarbon the mixture of solvents required a prolonged residence time to remove the dirt lubricant, i.e., the total cleaning of l m of soiled area required more than 3 minutes time and the application of mechanical power. Thus, it can be stated that the detergency power is rather high but that the dirt lubricant solving time is far too long, especially in view of the great areas to be cleaned.

Further tests showed that aliphatic, lower ketones, from which acetone is known as a solvent for certain resins, exhibit a much stronger and quicker solving efficiency for resins in admixture with the other ingredients (A), (B), and (D) than individual ketones. This synergetic effect was very much surprising and unpresumable.

Example 1 A mixture consisting of the following ingredients was examined:

25% methylene chloride 25% ethyl acetate 40% isopropanol [0% of a sulphonate of coconut fat alcohols.

The tiles to be cleaned were soiled with the abovementioned lubricant forming dirt composition and submitted to an ageing process of one year. By means of a cleaning cloth soaked with the above-mentioned detergent an area of tiles of l m was cleaned and rinsed with water in 30 sec. time. This detergency power of 30 seconds could be considered as very good.

A similar very good (30 seconds or less) detergency power was exhibited by the following combinations according to example 2 to 5.

Example 3-Continued lOVr monoethyanolamine salt of the sulphonated coconut fatty alcohols ether.

Example 4 Example 5 I07: methylene chloride 207: methyl ethyl ketone ethyl acetate 40% isopropanol 20 I07: sodium lauryl sulphate.

Example 6 methylene chloride ethyl acetate isopropanol of a sulphonate of coconut fat alcohols bezin of Kp. l3ll,l50C.

Example 7 Example 8 methylene chloride diethyl ketone ethyl acetate butanol monoethanolamine salt of the sulphonated coconut fatty alcohols ether.

Example 9 methylene chloride methyl ethyl ketone propyl acetate ethnaol triethanolamine salt of the lauryl alcohol sulphuric acid ester.

Example 10 The results obtained in Examples 1 to 10 could be considered as very good: the joints of the cleaned tiles did not show any changes and the lustre of the tiles remained unchanged. The expression "very good" at the end of the examples 1 to means that in the very short time of 30 seconds, the dirt had been soaked completely without any residue and could be washed away with water. The known prior art cleaning agents, however, are not able to solve analogous dirts consisting at the same time of lignite tar, motor oil recovered from waist oils and fats, and resins. The maximum allowable vapor concentration (in ppm or b/m of the detergent according to the invention is so high that they can be used without any operating safety risk.

In the following examples 11 to 14 the detergency power of combinations including perchloroethylene or trichloroethylene were examined. For this end methylene chloride from the composition accordingto example 5 was substituted by perchloroethylene or trichloroethylene. This composition required a longer residence time, the detergency power of the mixture, however, can be considered as good.

Example 1 l A mixture with the following ingredients:

107: trichloroethylene 20% methyl ethyl ketone 20% ethyl acetate 40% isopropanol [0% sodium lauryl sulphate showed a good detergency power; required, however, a much longer residence time than the compositions including methylene chloride according to the examples l to 10.

Similar compositions which had thefollowing ingredients showed the same results:

Example 12 10% perchloroethylene 207: methyl ethyl ketone 20% ethyl acetate 40% isopropanol 10% sodium lauryl Example 13 trichloroethylene methyl ethyl ketone ethyl acetate isopropanol sodium lauryl sulphate benzin of Kp. 120-l40C,

Example 14 perchloroethylene methyl ethyl ketone ethyl acetate isopropanol sodium lauryl sulphate Finally compositions with considerably changing concentrations of the ingredients were examined, i.e., compositions with a considerably higher or lower amount of methylene chloride, methyl ethyl ketone, ethyl aceate, surface active substances and alcohols according to examples 1 to 10. It was observed that within a great range dirt lubricant solubility is to be called good or very good, but that the residence time of the lubricants soaked by the solvent increases with a decreasing amount of methylene chloride, whereas the wettability of the dirty places increases with a rising amount of surface active substances.

TEST COMPARlSON REPORT 1n the following manner the superiority of the detergent compositions of the invention in comparison with the known detergents of comparable mixture was proved in the preceding and in the following comparative examples. On l m pottery tiles were subsequently spread 250 each of a. varnish of a polyacrylic resin b. a mixed styrene butadiene polymer c. a dispersion of polyvinyl acetate (1. lignitetar e. motor oil recovered from waist oils and fat, and submitted to an ageing process, comprising the following steps: for 12 hours the tiles were dryed by infrared light and aerated and then for 12 hours submitted to a relative humidity of657c at 20 C. The prepared tiles were then treated with each 250 g of the detergent in the composition of the invention and of the fluid detergentknown from the German published Pat. application No. 1,200,460. In the examples which follow, after 5 minutes time, we tried to remove the impurities with water. Out of the known detergents were applied those of example 1 (with perchloroethylene), 2 and 6 of the German published Pat. No. 1,200,460.

The composition of Example 1 of the German patent contains parts by weight of carbon tetrachloride or perchloroethylene and 20 parts by weight of a 80% technical alkyl benzene acid, neutralized with 15 parts by weight of crude pyridine.

The composition of Example 2 of the German patent contains 2320 parts by weight of perchloroethylene, parts by weight of a sulfated polyglycol ether of fat alcohol and 660 parts by weight of the abovementioned alkylbenzene sulfonic acid neutralized with 330 parts by weight of crude pyridine and parts by weight of morpholine.

The composition of Example 6 of the German patent contains 2,600 parts by weight of perchloroethylene, 1,000 parts by weight of decylphenolepolyglycolether and 390 parts by weight of a 80% dibutylnaphtalenesulfonic acid, which was neutralized with 100 parts by weight of pyridine.

These compositions were capable of solving only oils (e) and tars (d); only these tars and fats could be removed in the form of aqueous emulsions; varnishes, e.g. resins (a), (b) and (c) remained; however, unchanged and could not be removed. For comparison the following mixtures in the composition of the inven tion were applied:

g perchloroethylene g methylene chloride g methyl ethyl ketone g isopropanol g sodium lauryl sulphate.

by weight of methylene chloride by weight of butanone by weight of isopropanol by weight of sodium lauryl sulphate.

4) l2'7r by weight of methylene chloride 25% by weight of methyl ethyl ketone -Continued 50% by weight of isopropanol 13% by weight of sodium lauryl sulphate.

In the four cases all inpurities spread on the tiles could be solved quickly and removed easily with water.

The same results were obtained when cleaning spatulas, brushes, etc. soiled with oil, tar, paint and varnish. In most of the cases there was required a residence time of only 1 minute; set residues of resin, varnish and paint required depending on the hardening rate a longer residence time. The detergents of the German Pat. No. 1,200,460 and liquid hydrocarbon-based cleansing agents proved to be insufficient.

Therefore it can be seen that in general the known detergents which were used for comparison are effective at solving oil and fat but have no or only minor solving efficiency to solve varnish, paint and resin. In contrast the detergents of the present invention varnish, paint and resin easily. Thus, the detergents of the present invention are universal cleaning agents.

What is claimed is: l. A solvent-based detergent composition that is miscible with water consisting essentially of A. 10-80% by weight liquid aliphatic chlorinated hydrocarbons; B. 10-40% by weight liquid lower aliphatic ketones and/or liquid lower aliphatic esters; C. 550% by weight water-soluble alkanols having two to five carbon atoms and D. ll0% by weight of a detergent anionic or nonionic surface active agents. 2. The composition of claim 1, consisting essentially of A. 25% of said liquid aliphatic chlorinated hydrocarbons; B. 40% of said liquid aliphatic ketones and/or said liquid aliphatic esters; C. 40-50% of said water-soluble alkanols, and D. 1-10% of said surface active agents. 3. A detergent composition of claim 1, wherein said component A. is methylene chloride, trichloroethylene or perchloroethylene; B. is methyl ethyl ketone or ethyl acetate C. is isopropanol, propanol or butanol and D. is an anionic surface active agent.

4. A detergent composition of claim 1 wherein said chlorinated hydrocarbons are selected from the group consisting of monochloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane and tetrachloroethane.

5. A detergent composition of claim 1 wherein said ketone (B) is selected from the group consisting of diethyl ketone, methyl propyl ketone and isomeric ethyl butyl ketones.

6. A detergent composition of claim 1, wherein said esters (B) are selected from the group consisting of methyl acetate, propyl acetates. butyl acetates, methyl propionates. ethyl propionates, propyl propionates. butyl propionates, methyl butyrates, ethyl butyrates, propyl butyrates and butyl butyrates.

7. A detergent composition of claim 1, wherein said alkanols (C) are selected from the group consisting of ethanol and amyl alcohols.

8. A detergent composition of claim 1, wherein (A) is methylene chloride. (B) is ethyl acetate, (C) is isopropanol and (D) is a sulphonate of coconut fat alcohols.

9. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl propyl ketone, (C) is propanol and (D) is ammonium salt of sulphuric acid ester of lauryl alcohol.

10. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is diethyl ketone and ethyl acetate, (C) is butanol and (D) is moneethanolamine salt of the sulphonated coconut fatty alcohols ether.

11. A detergent composition ofclaim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and propyl acetate, (C) is ethanol and (D) is triethanolamine salt of the lauryl alcohol sulphuric acid ester.

12. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and ethyl acetate, (C) is isopropanol and (D) is sodium lauryl sulphate.

13. A detergent composition of claim 1, which also contains ll0% of a liquid hydrocarbon fraction having a boiling point of to C.

14. Cleaning surfaces soiled with oils, fats, tars, resins, asphaltenes, pitches, varnishes, paints or mechanical impurities with the composition of claim 1.

l l l l l= 

1. A SOLVENT-BASED DETERGENT COMPOSITION THAT IS MISCIBLE WITH WATER CONSISTING ESSENTIALLY OF A. 10-80% BY WEIGHT LIQUID ALIPHATIC CHLORINATED HYDROCARBONS; B. 10-40% BT WEIGHT LIQUID LOWER ALIPHATIC KETONES AND/OR LIQUID LOWER ALIPHATIC ESTERS; C. 5-50% BY WEIGHT WATER-SOLUBLE ALKANOLS HAVING TWO TO FIVE CARBON ATOMS AND D. 1-10% BY WEIGHT OF A DETERGENT ANIONIC OR NONIONIC SURFACE ACTIVE AGENTS.
 2. The composition of claim 1, consisting essentially of A. 10-25% of said liquid aliphatic chlorinated hydrocarbons; B. 25-40% of said liquid aliphatic ketones and/or said liquid aliphatic esters; C. 40-50% of said water-soluble alkanols, and D. 1-10% of said surface active agents.
 3. A detergent composition of claim 1, wherein said component A. is methylene chloride, trichloroethylene or perchloroethylene; B. is methyl ethyl ketone or ethyl acetate C. is isopropanol, propanol or butanol and D. is an anionic surface active agent.
 4. A detergent composition of claim 1 wherein said chlorinated hydrocarbons are selected from the group consisting of monochloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethane and tetrachloroethane.
 5. A detergent composition of claim 1 wherein said ketone (B) is selected from the group consisting of diethyl ketone, methyl proPyl ketone and isomeric ethyl butyl ketones.
 6. A detergent composition of claim 1, wherein said esters (B) are selected from the group consisting of methyl acetate, propyl acetates, butyl acetates, methyl propionates, ethyl propionates, propyl propionates, butyl propionates, methyl butyrates, ethyl butyrates, propyl butyrates and butyl butyrates.
 7. A detergent composition of claim 1, wherein said alkanols (C) are selected from the group consisting of ethanol and amyl alcohols.
 8. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is ethyl acetate, (C) is isopropanol and (D) is a sulphonate of coconut fat alcohols.
 9. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl propyl ketone, (C) is propanol and (D) is ammonium salt of sulphuric acid ester of lauryl alcohol.
 10. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is diethyl ketone and ethyl acetate, (C) is butanol and (D) is moneethanolamine salt of the sulphonated coconut fatty alcohols ether.
 11. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and propyl acetate, (C) is ethanol and (D) is triethanolamine salt of the lauryl alcohol sulphuric acid ester.
 12. A detergent composition of claim 1, wherein (A) is methylene chloride, (B) is methyl ethyl ketone and ethyl acetate, (C) is isopropanol and (D) is sodium lauryl sulphate.
 13. A detergent composition of claim 1, which also contains 1-10% of a liquid hydrocarbon fraction having a boiling point of 120* to 180* C.
 14. Cleaning surfaces soiled with oils, fats, tars, resins, asphaltenes, pitches, varnishes, paints or mechanical impurities with the composition of claim
 1. 